Detergent composition



United States Patent Ofitice 3,313,734 Patented Apr. 11, 1967 3,313,734DETERGENT COMPOSHTION Edward W. Lang, Cincinnati, and Homer W. McCune,Wyoming, Ohio, assignors to The Procter & Gamble Company, Cincinnati,Ohio, a corporation of Ghio No Drawing. Filed May 1, 1963, Ser. No.277,091 18 Claims. (Cl. 252152) This invention relates to an aqueousdetergent composition especially adapted for cleansing hair. Morespecifically, it relates to a homogeneous aqueous shampoo compositioncharacterized by its outstanding capacity to improve the condition ofhair.

A shampoo composition in order to be commercially acceptable must possescertain basic characteristics. For example, it must clean without undulydiminishing the natural lustre of the hair as by precipitation ofdulling insoluble soap films. It must be a stable, homogeneous productwhich will not separate under ordinary conditions of storage and usage.Further, it must yield a copious lather and must work well in hardwater.

With the advent of synthetic detergents, shampoo formulators havelargely overcome the more basic problems of shampoo development and arenow concerned with the provision of compositions which leave the hair ina manageable condition, since the removal of substantial proportions ofthe natural oil from the hair in the course of shampooing adverselyaffects hair manageability. Although measures have been taken in shampooformulation to prevent or alleviate this undesirable effect, as far asis known, none of these measures have succeeded without loss orimpairment of one or more of the forementioned basic characteristics ofcleaning, lathering, stability, etc.

Hair conditioning agents such as polyglycols, fatty acid esters ofglycols, natural or synthetic waxes and lanolin derivatives, forexample, have been added to shampoo formulations as a means ofcounteracting the detrimental eiiects of natural oil loss caused byshampooing the hair. Such materials can cause the hair to have anunpleasant oily appearance and feel. Further, certain hair conditioningagents, especially those of the oily nature mentoned above, inhibitsudsing of the shampoo. Consumers have come to expect copious latherfrom shampoo and are dissatisfied if it is not formed.

Products are, of course, available for application to the hairsubsequent to shampooing which are intended to counteract theundesirable eiiects of the shampoo on hair manageability and to improvethe condition of the hair in various respects. Hair rinses, sets andsprays have been developed which improve manageability and wave setretention. Such products often contain polymeric substances which form afilm on the hair upon drying, thereby holding the hair in a desiredpreformed configuration, i.e., increase wave set retention. As far as isknown, however, none of these polymeric materials have been incorporatedinto a satisfactory shampoo formulation. Generally these substances, ifsoluble enough to be included in a homogeneous shampoo product, are notof such a nature that they become substantively attached to the hairfiber to a degree sufiicient to prevent removal in the course of washingand rinsing.

The term hair manageability as used herein refers to the relative easewith which the hair can be placed in a desired coiffure. Factorsinfluencing hair manageability are hair lubricity and entanglement, i.e.combability, and electrostatic charge causing hair fly.

It is an vobject of this invention to provide a stable aqueous detergentcomposition especially adapted for cleansing the hair which improveshair manageability and wave set retention.

It is a further object of this invention to provide a stable aqueousshampoo composition which improves the wave set retention of the washedhair but which also possesses excellent cleansing and latheringcharacteristics.

It has now been found that certain quaternary ammonium-containingpolymers when employed in liquid detergent compositions containing amixture of anionic and ampholytic or polar nonionic detergents, formclear homogeneous liquids while in a concentrated product form, butprecipitate on the hair fiber when the product is diluted in the courseof usage. Upon drying this precipitate improves the wave retention ofthe hair and hair manageability. These concentrated formulations arestable and possess excellent cleaning and sudsing char acteristics whendiluted with water.

In general the compositions of this invention are comprised of fromabout 0.1% to about 7.0% of a watersoluble polymer at least 30 molepercent of the structure of which is composed of monomeric unitsselected from the group consisting of quaternized vinylimidazole,quaternized diethylaminoethyl methacrylate, quaternizeddimethylaminoethyl methacrylate, quaternizedp-dimethylaminomethylstyrene and combinations thereof, from about 0.1%to about 10.0% of an organic anionic detergent, from about 5.0% to about20.0% of a detergent selected from the group consisting of polarnonionic detergents, ampholytic detergents, and mixtures thereof, andthe balance substantially water, the weight ratio of anionic detergentto the polymeric component being not greater than about 10:1.Formulations encompassed by this invention are stable, homogeneouscompositions which as hereinbefore indicated yield a fine precipitate ofthe polymer component upon dilution with water. The precipitate adheresfirmly to the hair shaft in the course of lathering and rinsing and doesnot appreciably change the appearance of the hair on drying. Theadherent material produces the improved hair manageability and wave setretention of this invention.

The polymeric compounds which can be used in the compositions of thisinvention are characterized by possessing a net positive charge which isimparted by the substantial proportions of quaternary ammonium groupscontained therein. At least about 30 mole percent of the total polymericstructure must be composed of the herein described monomeric unitscontaining such groups. If the polymer contains less than about 30 molepercent of these monomeric units, the net positive charge of the polymerwill not be great enough to cause the polymer to precipitate and adhereto the hair with sufiicient force to prevent removal by the detergentcomponents. Preferably, the polymer will be comprised of monomeric unitsat least 50 mole percent of which are the quaternary ammonium-containingmonomeric units disclosed herein.

It can be seen that polymers encompassed by the foregoing descriptioncan be either homopolymers of quaternizable units at least 30 molepercent of which are in fact quaternized, or copolymers containing atleast 30 mole percent of quaternizable units, the balance of the polymerbeing composed of non-quaternizable units, at least 30 mole percent ofthe quaternizable units being quaternized.

The molecular weight of the polymeric component is not critical;however, the preferred polymers have an average molecular weight withinthe range from about 1000 to 5,000,000. Polymers having a molecularweight of less than about 1000 may not precipitate from the compositionsof this invention in the course of shampooing to impart the desired Waveset retention properties. Polymers having molecular weights in excess of5,000,000 may not be sufliciently soluble to provide a stable homogenousproduct. Preferably the molecular weight of the polymers employed in thecompositions of this invention will be greater than about 4000.

The concentration of the polymeric component can vary according to theamount of film deposition desired. Amounts below about 0.1% will notordinarily yield improved manageability and wave set retention.Concentrations greater than about 7.0% yield an undesirably heavy andsomewhat sticky film on the hair. Preferably, this component will beemployed in a concentration of from about 0.5% to about 5.0% by weightof the total composition.

In general, the quaternary ammonium polymers employed in thecompositions of this invention can be prepared by quaternizing thetertiary nitrogen-containing neutral polymer or copolymer to give apositively charged polymer neutralized by low molecular weight anions.Alternatively, these polymers can be prepared by quaternizing thetertiary nitrogen-containing monomer and then polymerizing thequaternized monomer, alone or with another suitable polymerizable unitas described hereinafter. The tertiary amine or quaternaryammonium-containing monomers are polymerized by reactions promoted byheat, with or without a catalyst present.

Any quaternizing agent which will not substantially change the nature ofthe finally resulting polymer (e.g. which does not greatly decrease itssolubility or greatly increase its reactivity) can be employed in thepreparation of suitable polymers. Those agents which provide a lowmolecular weight quaternizing group and anion are preferred from thisstandpoint. For example, benzyl halides such as benzyl chloride, andshort chain alkyl halides such as methyl iodide, ethyl bromide and butylchloride; short chain alkyl sulfates such as dirnethyl sulfate; shortchain alkyl sulfonates such as ethyl ptoluene sulfonate; alkylphosphates such as triethyl phosphate; and alkyl phophites such astriethyl phosphite, are suitable quaternizing agents for preparing thequaternary ammonium-containing polymers to be employed in thecompositions of this invention.

It should be understood that in the immediately following disclosure theidentity of the anions which neutralize the charges of the quaternaryammonium polymers is not critical and depends upon the quaternizingagent employed and, in some cases, the conditions during and followingquaternization (e.g. methyl sulfate may be entirely or partly hydrolyzedto sulfate, S05).

A preferred quaternary ammonium-containing polymer for the purpose ofthis invention is polyvinylimidazole quaternized, for example, withdimethyl sulfate, and having the following structural formula (amonomeric unit being represented within the brackets):

wherein x is preferably an integrer of sufficient magnitude to yield apolymer having a molecular weight within the range from about 1000 to5,000,000. Such a polymer is prepared as follows:

86 parts of maleic acid diethyl ester and 47 parts of N-vinyl imidazoleare dissolved in 200 parts of dioxane and mixed with 6 parts of 30%hydrogen peroxide. The polymerization is accomplished in the course ofhours at a temperature of 70 to 80 C. Then 63 parts of di methyl sulfateare added dropwise to the solution of the resulting polymer. The productis a viscous precipitate which is separated from the supernatant dioxaneby conventional means. Quaternization is essentially complete, thussubstantially all of the polymer is composed of the monomeric unitsdepicted above. The molecular weight of the polymer is between 5000 and20,000.

4 Methods of preparing polymers of this general structure are furtherdisclosed in German patents 941,999, granted Apr. 26, 1956, and 847,347,granted Aug. 21, 1952.

Another polymer for use in the compositions of this invention isquaternized poly(diethylarninoethyl methacrylate) having the structuralformula:

Lu J.

XCHZOSO;

xHzP 04" NCH CH CH wherein x is preferably an integer of sufiicientmagnitude to yield a polymer having a molecular weight within the rangefrom about 1000 to about 5,000,000.

Still another group of polymers which is suitable for use in thecompositions of this invention is quaternizedpoly(p-dimethylaminomethylstyrene) which is comprised of units of thestructural formula:

wherein x is preferably an integer of sufficient magnitude to yield apolymer having a molecular weight within the range from about 1000 toabout 5,000,000, the bracketed structure being a monomeric unit.

In addition to the quaternary ammonium containing monomeric unitsdescribed herein, the polymers can contain up to 70 mole percent of oneor more non-quaternized monomeric units derived from monoethylenicallyunsaturated groups. Such groups conform to the structural formulawherein R is hydrogen, methyl, ethyl or phenyl and X is phenyl,substituted phony? -COOR', COONH OR", or CEN, wherein R is alkyl,

CH3 C2115 and R" is alkyl, including for example acrylonitrile, thevinyl aromatic compounds, more particularly the vinyl or othermonoethylenically unsaturated substituted aromatic hydrocarbons (e.g.,styrene, a-methylstyrene, the various dialkyl styrenes, etc.) otheraliphatic compounds containing a CH C grouping, e.g., the varioussubstituted acrylonitriles (e.g. methacrylonitrile, ethacr lonitrile,phenylacrylonitn'le, etc.) acrylamide and the various substitutedacrylamides (e.g., methacrylamide, ethyacrylamide); vinyl esters, e.g.,vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate,vinyl valerate, etc.; esters of an acrylic acid (including acrylic aciditself and the various tit-substituted acrylic acids, e.g., methacrylicacid, ethacrylic acid, phenylacrylic acid, etc.), more particularly thealkyl esters of an acrylic acid, e.g., the ethyl, propyl, isopropyl,n-butyl, isobutyl, sec-butyl, tert-butyl, amyl, hexyl, heptyl, octyl,decyl, dodecyl, etc. esters of acrylic, methacrylic, ethacrylic,phenylacrylic, etc. acids; vinyl ethers, such as butyl vinyl ether;N-vinyl compounds such as 1 -vinyl pyrrolidone; and olefins, such asethylene; fiuorinated vinyl compounds, such as vinylidene fluoride, aswell as other vinyl aromatic and vinyl aliphatic compounds, and otherswhich will not substantially alter the nature of the resultant polymer.

A preferred copolymer for use in the present invention is a copolymer ofapproximately equimolar proportions of vinylbenzyltrimethyl ammoniumchloride and acrylamide which can be prepared in accordance with themethods set forth in Canadian Patent 587,240, granted Nov. 17, 1959.

The organic anionic detergent which is employed in this inventionincludes both Water-soluble soap and nonsoap synthetic detergents.Operable non-soap anionic organic detergents include, for example,water-soluble salts of organic sulfuric reaction products having intheir molecular structure an alkyl group containing from about 8 toabout 20 carbon atoms and a radical selected from the group consistingof sulfuric acid and sulfonic acid ester radicals. Important examples ofthis type of non-soap anionic synthetic detergent, include the sodium orpotassium alkyl sulfates, especially these derived by sulfation ofhigher alcohols produced by reduction of glycerides of tallow or coconutoil; sodium or potassium alkylbenzene sulfonates, especially those ofthe types described by Guenther et al. in US. Patent 2,220,099, grantedNov. 5, 1940, and by Lewis in U.S. Patent 2,477,383, granted July 26,1949, in which the alkyl group contains from about 9 to about carbonatoms; sodium alkylglycerylether sulfonates, especially those ethers ofhigher alcohols obtained from tallow and coconut oil; sodium coconut oilfatty acid monoglyceride sulfates and sulfonates, sodium salts ofsulfuric acid esters of the reaction product of one mole of a higherfatty alcohol (e.g., tallow or coconut oil alcohols) and about 3 molesof ethylene oxide; and others well known in the art, a number beingspecifically set forth in Byerley U.S. Patent 2,486,921, granted Nov. 1,1949, and Strain, U.S. Patent 2,486,922, granted Nov. 1, 1949.

Preferably the non-soap anionic organic detergent will be of the highsudsing type as for example, the alkylglycerylether sulfonates, thesulfated fatty alcohols or the alkyl ether ethylene oxide sulfateswherein the ethylene oxide chain averages 3 units as more fully setforth above. These and the foregoing detergents can be used in the formof their sodium, potassium or lower alkanolamine such as triethanolaminesalts.

Soaps which may be used in the composition of this invention include thesodium and potassium salts of the higher fatty acids of naturallyoccurring vegetable or animal fats and oils. For example, sodium andpotassium salts of fatty acids occurring in coconut oil, soy bean oil,castor oil, tallow or synthetically produced fatty acids may be used.

The anionic organic detergent can be employed in concentrations rangingfrom about 0.1% to about 10% by weight of the total composition but mustnot exceed a weight ratio of 10:1 with respect to the quaternaryammonium-containing polymeric component. Preferably the organic anionicdetergent will be employed in a Weight ratio of about 4:1 to 1:4 to thequaternary ammonium-containing polymeric component. Because of thesuperior solubility and lathering properties of anionic detergentscontaining predominantly C and C alkyl chain lengths, these arepreferred for the purpose of this invention.

It is essential that the compositions of this invention contain at leastone member selected from the group consisting of polar nonionic andampholytic detergents. This component serves to compatibilize thepolymeric component and the anionic detergent. It further enhances thelathering and cleaning properties of the composition. By polar nonionicdetergent i meant a detergent in which the hydrophylic group contains asemipolar bond directly between two atoms e.g., N+O, P O, Ase O, and 8-0. There is charge separation between the two directly bonded atoms butthe detergent molecule bears no net charge and does not dissociate intoions. The polar nonionic detergents which can be used in conjunctionwith or as an alternative to the ampholytic detergent includes amineoxides of the general formula The arrow i a conventional representationof a semipolar bond. These compounds are generally prepared by thedirect oxidation of the appropriate tertiary amine. When R is a muchlonger chain than R and R the amine oxides have surface activity. Forthe purpose of this invention R is an alkyl radical having from 10 to 16carbon atoms. Desirable surface active properties are lost if R issubstantially less than 10 carbon atoms, and the compounds areinsufficiently soluble if R is greater than 16 carbon atoms. R and R areeach selected from the group consisting of methyl and ethyl radicals.Preferably R is a dodecyl radical or a mixture of dodecyl with decyl,tetradecyl and hexadecyl, such that at least 50% of the radical aredodecyl radicals. R and R are preferably methyl radicals. A preferredamine oxide for the purpose of this invention is dodecyldimethylamineoxide.

Other operable polar nonionic detergents are the phosphine oxides havingthe general formula wherein R is an alkyl, alkenyl or monohydroxyalkylradical ranging in chain length from 10 to 18 carbon atoms, and R and Rare each alkyl and monohydroxyalkyl radicals containing from 1 to 3carbon atoms. A preferred phosphine oxide is dodecyldimethyl phosphineoxide. This and other phosphine oxides together with a method ofpreparation are fully described by Yoke et al. in copending applicationSer. No. 173,834, filed Feb. 16, 1962.

As hereinbefore stated, ampholytic detergents can be used in conjunctionwith or in place of the polar nonionic detergents described above.Ampholytic detergents are well known in the art and many operabledetergents of this class are disclosed by A. M. Schwartz, J. W. Perryand J. Birch in Surface Active Agents and Detergents, IntersciencePublishers, New York, 1958, vol. 2. Examples of suitable ampholyticdetergents include, for example, alkyl beta-iminodipropionates, RN(C HCOOM) alkyl beta-amino propionates, RN(H)C H COOM; and long chainimidazole derivatives having the general formula:

CHI: lfil' (II-I RO--NCII CHgOCH;COOM

OH CHicooM In each of the above formulae R is an acyclic hydro phobicgroup containing from about 8 to about 18 carbon atoms and M is a cationto neutralize the charge of the anion. Specific operable ampholyticdetergents include the disodium salt oflauroylcycloimidinium-lethoxyethionic acid-Z-ethionic acid, dodecyl betaalanine, and the inner salt of Z-trimethylamino lauric acid. Thesubstituted betaines, such as alkyl ammonio acetates wherein the alkylradical contains from about 12 to about 18 carbon atoms can also beused. Several examples and a more complete description of this class ofampholytic detergents is set forth in the copending application ofSmith, Ser. No. 80,991, filed Jan. 6, 1961. The betaine and sultainetypes of ampholytic detergents are zwitterionic quaternary ammoniumcompound having the general formula:

wherein R is an alkyl radical having from about 10 to about 18 carbonatoms, R and R are each alkyl radicals having from about 1 to about 3carbon atoms, R.,, is an alkylene or hydroxyalkylene radical having from1 to 4 carbon atoms, and X is an anion selected from the groupconsisting of S and COO radicals.

Compounds which conform to the above general 'formula are characterizedby the presence of both positive and negative charges which areinternally neutralized (i.e. zwitterionic). When the anion X is 80 thesecompounds are referred to as sultanes. The term betains is employed whenthe anion X isCOO=. The following structural formulae are illustrativeof the two types and their inner salt character.

When one R in the above formulae is a high molecular alkyl radicalhaving from about to 18 carbon atoms, these compounds are surface activeand have good detergency powers. If the high molecular alkyl radicalcontains less than about 10 carbon atoms, surface activity anddetergency are inadequate. If this radical contains more than about 18carbon atoms, the compounds are not sufficiently soluble to be ofutility in this invention. Preferably, the high molecular alkyl radicalwill contain from 12 to 16 carbon atoms or a mixture of dodecyl withdecyl, tetradecyl and hexadecyl radicals. A convenient source of asuitable mixture of alkyl radicals is the middle cut of coconut fattyalcohol which has the approximate chain length composition: 2%-C 66%- C23%-C and 9%-C Particular advantage can be gained by employing a betaineor sultaine having an alkyl group containing 16 carbon atoms in thecompositions of this invention as will be illustrated infra. The alkylradical can, of course, contain one or more intermediate linkages suchas ether or polyether linkages or non-functional substituents such ashydroxyl or halogen radicals which do not substantially affect thehydrophobic character of the radical.

Preferred compounds which fall within the above class include1(alkyldimethylarnmonio) acetate, l-(alkyldimethylammonio)propane-3-sulfonate and 1(alkyldimethylammonio)2-hydroxy-propane-3-sulfonate wherein the a kyl group contains from 12to 16 carbon atoms.

The amine oxides are particularly advantageous for use in the presentinvention because of their superior capacity to compatibilize the othercomponents of the compositions and their high lathering, cleaning andsolubility characteristics.

Whether the polar nonionic detergents or ampholytic detergents areemployed in the compositions of this invention, their concentration inthe total composition will range from about 5% to about 20% by weight.Preferably this component will be employed at a concentration within therange of about 7% to about 15%.

Each of the forementioned components will be incorporated into anaqueous vehicle which may, in addition, include such materials asorganic solvents, thickeners, perfumes, sequestering agents andop-acifiers which are useful in enhancing the cosmetic properties ofshampoo formulations.

The term coconut as used in the following examples refers to alkylgroups which are derived from middle cut coconut alcohol having thefollowing approximate chain length distribution: 2%-C 66%-C 23%- C14 and9%"C1 Example I A liquid detergent composition was prepared having thefollowing composition:

Percent Dimethyl sulfate quaternized polyvinylimidazole 1 1.6Triethanolamine coconut sulfate 1.8 Coconut dimethylamine oxide 5.0Water Balance 1 The polymer was wa ter-soluble. had a molecular weightof from 5 to 2O 1O and consisted substantially entirely of quaternizedmonomeric units.

This composition was a clear stable liquid which yielded copious latherin the course of normal usage in shampooing the hair and left the hairin highly manageable state after washing. In order to evaluate the hairset retention characteristics imparted by the shampoo, a 2 g. testswitch of hair was Washed with 1 g. of this composition. The hair wasthen rinsed and placed into a curl configuration while still wet. Afterdrying, the degree of curl retention was compared with the degree ofcurl retention attained with the same quantity of a conventionalcommercially available shampoo employed in like manner on a test switchof the same hair. The composition of this example was found to bemarkedly superior in this respect.

The coconut dimethylamine oxide employed in this example can be replacedwith dodecyldimethylphosphine oxide with no substantial change inproduct characteristics or results achieved in use.

Example 11 An additional shampoo formulation was prepared having thefollowing composition:

Percent Dimethyl sulfate quaternized poly(diethylaminoethylmethacrylate) 1 3.0 Triethanolamine coconut sulfate 2.5 Coconutdimethylamine oxide 10.0 Water Balance Prepared in accordance withExample I of U.S. Patent 2,723,206. This polymer was water-soluble. andhad a molecular weight within the range from about 1000 to about 5,000,-000. I he polymer consisted essentially entirely of quaternaryammonium-containing units,

This composition was found to be a clear stable liquid which possessedthe same excellent cleaning and lathering characteristics of acommercially available shampoo when used to wash hair in theconventional manner. In addition, test switches of hair washed with thiscomposition 9 were left in a highly manageable condition, i.e., easilycombed and very little hair fly. The washed hair was tested for waveretention as in Example I. Curls formed after washing with thecomposition of this example were 10 employed in this example can bereplaced by a polymer of the same structure but having an averagemolecular weight of 100,000 or 750,000 without loss of the desiredproperties. So also, the concentration of the polymer retained for amuch greater length of time than curls employed in this example can bereduced to 0.5% by formed after washing test switches of the same hairwith weight and the desired performance characteristics Will aconventional shampoo. still be observed.

tflethall9lamlne coconut Sulfate be f p Table I below sets forth severaladditional shampoo Wlth Potasslum saltflf Coconut fatty aclds f f aformulations which were prepared in accordance with substantial loss ofdesired performance characteristics. the invention, lif i additionalpermissible -1 {5150, F P y f Fomponent replaced Wlth one tions incomposition. The polymeric components desig- 111 which quaternizationhas been lllIllted so that only 50 Hated A B, C, and D are,respectively, polyvinylimidazole mole p f of the monomeric umts contalnafluaternafy quaternized with dimethyl sulfate (same as Example I),ammonium group, wlthollt Fllbstantlany altering P poly(diethylaminoethylmethacrylate) quarternized with of Performance Charactenstlcsdimethylsulfate (same as Example II), poly(dimethyl aminoethyl methacrylate)quaternized with methyl phos- Example HI phate (a water-soluble polymerhaving a molecular weight Percent between 1000 and 5,000,000 andconsisting substantially Dlmfifthyl Sulfate quatemlzed P Y Y entirely ofmonomeric units containing a quaternary amirnidazole 2.0 20 moniurngroup), and the copolyrner of equimolar propor- Triethano a m o o tSulfate tions of vinylbenzyltrimethyl ammonium chloride and Lam Y Yl -lly acrylamide (a water-soluble, polymer having a molecularacid-Z-ethronic acid, disodium 10.0 Weight of the order of 500,000 andcontaining approxi- Water Bal n mately mole percent of quaternaryammonium-con- 1 Same as Example I. taining monomeric units).

TABLE I Example Component V VI VII VIII IX X XI XII Polymer A. 2. 5 2.02. 0 2.0 3. 0 Polymer B 3.0 Polymer G- 3. 0 Polymer D. 3.0 Lauroylcycloimidiniurn-l-ethoxyethionic-acid-2-ethionic acid, disodium 10.010.0 Coconutdimetliyl' min oxide 10. 0 l0. 0 10. 0 10. 0 Cetyl bet'iine10. 0 10. 0 Triethanolarumonium coconut sull'ate- 3.0 Sodium salt ofsulfated condensation product of 1 mole of coconut alcohol with 3 molesof ethylene oxide 5. 0 5. 0 5.0 Tricthanolanunoniurn alkyl benzene Su flSodium coconutallrylglycerylether sulfomtp Sodium coconut monoglyceridesulfouate. 0.5 Alcohol 10.0 10.0 10.0 10.0 Water 1 All-:yl group is amixture of tri-, tetraand pentapropylene and has an average carbon atomscontent of about 12.

2 Balance.

Example IV Percent Dimethyl sulfate quaternized polyvinylimidazole 1Sodium salt of sulfated condensation product of 1 mole of coconutalcohol with 3 moles of ethylene oxide 0.95 Coconut dimethylamine oxide7.5 Water Balance 1 Same as Example I.

The above composition was a clear homogeneous liquid which remainedstable after prolonged storage. Hair washed with this composition in theconventional manner was found to be highly manageable and retained adesired configuration for substantial periods of time.

The dirnethyl sulfate quaternized polyvinylimidazole Each of theforegoing compositions was a stable homogeneous liquid. Each yieldedcopious lather when used in normal concentration in water to wash testswitches of hair. The test switches were wrapped upon a mandrel afterwashing and permitted to dry. The curl formed thereby was found to beretained, even under humid conditions, for substantial periods of time.

Polymer D of Example VIII can be replaced by a quaternizedpoly(p-dimethylaminomethylstyrene) having a molecular weight of 250,000and consisting essentially entirely of quaternized monomeric units withno substantial loss of desired product and performance characteristics.

The precipitate which forms in the course of shampooing with thecompositions of this invention may be removed if desired by shampooingthe hair with an ampholytic detergent, for example.

Percentage values employed in the specification and claims refer topercent by weight of the total composition unless otherwise stated.

What is claimed is:

1. An aqueous detergent composition especially adapted for use inshampooing hair consisting essentially of (a) from about 0.1% to about7.0% of a water-soluble polymer at least 30 mole percent of themolecular structure of which is composed of monomeric units selectedfrom the group consisting of quaternized vinylimidazole, quaternizeddiethylaminoethyl methacrylate, quaternized dimethy-laminoethylmethacry-late, quaternized p-dimethylaminomethylstyrene and combinationsthereof, any balance of said polymer being composed of non-quaternizedmonomeric units derived from monoethylenically unsaturated groups, saidpolymer having a molecular weight within the range from about 1000 toabout 5,000,000, (b) from about .1% to about 10% of a water-soluble saltof a higher fatty acid or an anionic organic sulfuric reaction producthaving in its molecular structure an alkyl group containing from about 8to about 20 carbon atoms and a sulfuric acid or sulfonic acid esterradical, (c) from about to about 20% of a member selected from the groupconsisting of polar nonionic detergents, ampholytic detergents havingthe structural formula wherein R is an acyclic hydrophobic groupcontaining from about 8 to about 18 carbon atoms and M is a cation toneutralize the charge of the anion; or

wherein R is an alkyl radical having from about to about 18 carbonatoms, R and R are each alkyl radicals having from about 1 to about 3carbon atoms, R,

is an alkylene or hydroXy-alkylene radical having from 1 to 4 carbonatoms and X is SO or COO=; and mixtures thereof, and the balancesubstantially ((1) water, the weight ratio of component (b) to component(a) being not greater than about 10 to 1.

2. The composition of claim 1 wherein the polymer is a substantiallycompletely quaternized polyvinylimidazole.

3. The composition of claim 1 wherein the polymer is a substantiallycompletely quaternized poly(diethylaminoethyl methacrylate).

4. The composition of claim 1 wherein the polymer is a substantiallycompletely quaternized poly(dimethylaminoethyl methacrylate).

5. The composition of claim 1 wherein the polymer is a substantiallycompletely quaternized poly(p-dimethylaminornethylstyrene) 6. Thecomposition of claim 1 wherein the polymer is a copolymer of equimolarquantities of vinyl'benzyltrimethyl ammonium chloride and acrylamide.

7. An aqueous detergent composition especially adapted for use inshampooing hair consisting essentially of (a) from about 0.5% to about5.0% of a Water-soluble polymer at least 30 mole percent of themolecular structure of which is composed of monomeric units selectedfrom the group consisting of quaternized vinylimidazole, quaternizeddiethylaminoethyl methacrylate, quaternized dimethylaminoethylmeth-acrylate, quaternized p-dimethylaminomethylstyrene and combinationsthereof, any balance of said polymer being composed of non-quaternizedmonomeric units derived from monoethylenically unsaturated groups, saidpolymer having a molecular weight within the range from about 1000 toabout 5,000,000, (b) from about 0.1% to about 5.0% of a water-solublesalt of an anionic sulfuric reaction product having in its molecularstructure an alkyl group containing from about 8 to about 20 carbonatoms and a radical selected from the group consisting of sulfonic andsulfuric acid ester radicals, (c) from about 7% to about of a polarnonionic detergent, and the balance 12 substantially (d) water, theweight ratio of component ('b) to component (a) being within the rangefrom about 1:4 to about 4: 1.

8. The composition of claim 7 wherein the watersoluble salt of ananionic sulfuric reaction product is an alkylgly cerylether sulfonate,neutralized by an anion selected from the group consisting of sodium,potassium and triethanolammonium.

9. The composition of claim 7 wherein the watersoluble salt of ananionic sulfuric reaction product is a sulfated condensation product of1 mole of coconut fatty acids and 3 moles of ethylene oxide, neutralizedby an anion selected from the group consisting of sodium, potassium andtriethanolammonium.

10. The composition of claim 7 wherein the watersoluble salt of ananionic sulfuric reaction product is an alkylbenzene sulfonate,neutralized by an anion selected from the group consisting of sodium,potassium and triethanolammonium.

11. The composition of claim 7 wherein the polar nonionic detergent isan amine oxide of the general formula R R R N O where R is an alkylradical having from 10 to 16 carbon atoms and R and R are each selectedfrom the group consisting of methyl and ethyl radicals.

12. The composition of claim 7 wherein the polar nonionic detergent is aphosphine oxide of the general formula R R R P O where R is an alkylradical having from 10 to 18 carbon atoms and R and R are each selectedfrom the group consisting of alkyl and monohydroxyalky-l radicals havingfrom 1 to 3 carbon atoms.

13. An aqueous detergent composition especially adapted for use inshampooing hair consisting essentially of (a) from about 0.5% to about5.0% of a water-soluble polymer at least 30 mole percent of themolecular structure of which is composed of monomeric units selectedfrom the group consisting of quaternized vinylimidazole, quaternizeddiethylarninoethyl methacrylate, quaternized dimethylaminoethylmethacrylate, quaternized p-dimethylaminomethylstyrene and combinationsthereof, any balance of said polymer being composed of non-quaternizedmonomeric units derived from monoethylenically unsaturated groups, saidpolymer having a molecular weight within the range from about 1000 toabout 5,000,000, (b) from about 0.5% to about 5.0% of a water-solublesalt of an anionic organic sulfuric reaction product having in itsmolecular structure an alkyl group containing from about 8 to about 20carbon atoms and a radical selected from the group consisting ofsulfonic and sulfuric acid ester radicals, (c) from about 7% to about15% of an ampholytic detergent having the structural formula RN(CH.;COOM) RN(H)C H COOM;

/CE2 i r R-C N CHzCHzOCI-IzCOOIlI I OH cHicooM wherein R is an acyclichydrophobic group containing from about 8 to about 18 carbon atoms and Mis a cation to neutralize the charge of the anion; or

15. The composition of claim 13 wherein the am- References Cited by theExaminer pholytic detergent is dodecyl beta alanine.

16. The composition of claim 13 wherein the am- UNITED STATES PATENTSpholytic detergent is the inner salt of Z-trimethylamine 2,723,256 11/1955 Hayek 260-79.3 lauric acid. 5 2,741,568 4/1956 Hayek 252-8.8 X

17. The composition of claim 13 wherein the anionic 2,965,594 12/ 1960Maeder 2528.8 X organic sulfuric reaction product is tn'eth-auola-minecoconut sulfate- LEON D. ROSDOL, Primary Examiner.

18. The composition of claim 13 wherein the anionic organic sulfuricreaction product is the sodium salt of a 10 JULIUS GREENWALD,Exammersulfated condensation product of mole of coconut al- I T.FEDIGAN, Assistant Examiner cohol with 3 moles of ethylene oxide.

1. AN AQUEOUS DETERGENT COMPOSITION ESPECIALLY ADAPTED FOR USE INSHAMPOOING HAIR CONSISTING ESSENTIALLY OF (A) FROM ABOUT 0.1% TO ABOUT7.0% OF A WATER-SOLUBLE POLYMER AT LEAST 30 MOLE PERCENT OF THEMOLECULAR STRUCTURE OF WHICH IS COMPOSED OF MONOMERIC UNITS SELECTEDFROM THE GROUP CONSISTING OF QUATERNIZED VINYLIMIDAZOLE, QUATERNIZEDDIETHYLAMINOETHYL METHACRYLATE, QUARTERNIZEDDIMETHYLAMINOETHYLMETHACRYLATE, QUATERNIZED P-DIMETHYLAMINOMETHYLSTYRENE AND COMBINATIONS THEROF, ANY BALANCE OF SAID POLYMERBEING COMPOSED OF NON-QUATERNIZED MONOMERIC UNITS DERIVED FROMMONOETHYLENICALLY UNSATU RATED GROUPDS, SAID POLYMER HAVING A MOLECULARWEIGHT WITHIN THE RANGE FROM ABOUT 1000 TO ABOT 5,000,000, (B) FROMABOUT .1% TO ABOUT 10% OF A WATER-SOLUBLE SALT OF A HIGHER FATTY ACID ORAN ANIONIC ORGANIC SULFURIC REACTION PRODUCT HAVING IN ITS MOLECULARSTRUCTURE AN ALKYL GROUP CONTAINING FROM ABOUT 8 TO ABOUT 20 CARBONATOMS AND A SULFURIC ACID OR SULFONIC ACID ESTER RADICAL, (C) FROM ABOUT5% TO ABOUT 20% OF A MEMBER SELECTED FROM THE GROUP CONSISTING OF POLARNONIONIC DETERGENTS, AMPHOLYTIC DETERGENTS HAVING THE STRUCTURAL FORMULA